Process fob preparing wetting



UNITED STATES deference PATENT OFFICE PROCESS FOR PREPARING WETTINGSUDSING,

EMULSIFYING, AND

nati, Ohio, assignors to Company, Cincinnati, Ohio The Procter & GambleOhio, a corporation of No Drawing. Application January 18, 1936, SerialNo. 59,790

12 Claims.

This invention relates to an improved process for preparing wetting,sudsing, emulsifying and detergent agents consisting of salts ofsulfated higher alcohols.

Its object is to prepare these materials by using only a dry solidreagent as described below which converts the alcohol to the salt of thesulfated alcohol in a single reaction.

This application is a companion case to our application Serial No.646,708, filed December 10, 1932 and issued as U. S. Patent No.2,049,670 on August 4, 1936, and it is also related to our copendingapplication Serial No. 59,789, filed January 18, 1936, which is directedspecifically to preparing wetting, sudsing, emulsifying and detergentagents of exceptional efliciency from unsaturated higher aliphaticalcohols by sulfating them with a reagent prepared by the reaction ofsulfur trioxide on metal chlorides or of chlorsulfonic acid on metalchlorides or sulfates.

It is well known that good wetting, sudsing, emulsifying and detergentagents can be prepared from the higher aliphatic alcohols, especiallythose containing from about ten to twentytzvo carbon atoms per moleculein two stages, by first sulfating the alcohols and then neutralizing thesulfuric esters thus formed. In the past the sulfation reaction hasalways been carried out by treating the alcohols with liquid reagents,such as concentrated sulfuric acid, fuming sulfuric acid, orchlorsulfonic acid, all of which are liquids of highly corrosive nature.This reaction must be carried out in acid proof liquid-tight vessels andthere is always danger from leakage or spillage in handling suchliquids, and especially in carrying out the sulfation reaction itselfdue to frothing. The sulfuric acid esters thus formed must next beneutralized, which is usually accomplished by adding the esters to anaqueous solution of caustic alkali, another liquid of corrosive nature,which thus adds to the danger from possible leaks and spills.

We have discovered that good wetting, sudsing, emulsifying and detergentagents can be made from the higher aliphatic alcohols containing 7,

from about ten to twenty-two carbon atoms per v molecule without the useof corrosive liquids either in the sulfation or neutralization steps, bytreating said higher alcohols with a solid reagent in powder form,described herein, which directly converts the alcohols to the neutralsalt of the sulfuric esters of the alcohols. Solvents are unnecessary inthe present process. Neutralization of any excess reagent used isreadily accomplished in our process by the further addition of a solidbasic or alkaline reagent as described below.

The reagent which we use may be produced by causing chlorsulfonic acidto react with either the chloride or sulfate of a metal such as sodium,potassium, ammonium, cobalt, manganese, etc.

The reagent thus obtained probably consists largely of thechlorsulfonate of the metal, although its actual composition need not bedefinitely established. We prefer to use a metal which forms a sulfationproduct which is at least moderately soluble in water, sodium,potassium, magnesium, and manganese being especially desirable.

For making wetting, sudsing, emulsifying and detergentag'eritsweu'sepreferably those higher aliphatic alcohols containing fromabout ten to twenty-two carbon atoms per molecule. The higher alcoholscorresponding to the fatty acid radicals of natural fats and oils, andprepared by catalytic reduction of such fats and oils, are especially tobe desired for our process; coconut oil, palm kernel oil and similaroils characterized by a high saponiflcation value are especiallysuitable, and are substantial equivalents for the purpose of our processand products. Alcohols obtained from other sources, such as thesaponification of sperm oil and the oxidation of paraffin hydrocarbonsmay also be used; the latter, however, consist largely of secondaryalcohols and do not make as good detergent products in general as thecorresponding primary alcohols unless especially purified.

Alcohols from sperm oil are in the main unsaturated and we have in acompanion application (Ser. No. 59,789, filed January 18, 1936) coveredour discovery herein disclosed so far as it applies to the unsaturatedalcohols. In this specification and claims the term fat includes anynatural fat or fatty oil, whether of vegetable or animal origin.

In preparing our reagent we mix commercial chlorsulfonic acid withsodium chloride or sulfate or corresponding salt of other metal at roomtemperature. A vigorous reaction ensues with a rise of temperature, andevolution of hydrochloric acid gas when chlorides are used. Thetemperature is preferably kept below about 50 C., as side reactions takeplace at higher temperatures with evolution of chlorine in some cases.This product is also a solid in powder form, or easily reducible to apowder.

Moisture must be excluded as moisture decomposes these reactlonproducts. An excess of the dry salt (NaCl, Naz S04, etc.) in preparingthe UUCU UH HU'JH reagent is desirable in the reagent as used, as itmakes a more friable reaction mixture which is more easily mixed andground. The excess may conveniently be from twenty-five per cent to one5 hundred per cent of the calculated quantity.

It will benoted that the chlorsulfonic acid is used only to react withthe solid chloride or sulfate and not with the alcohol, so that nofrothing of the corrosive acid occurs with its attendant danger, such asoccurs when sulfating the alcohol with this reagent. Of course in thesulfation of the alcohols the reagent is a solid, so that our method hasbeen termed a dry sulfation, the only fluid present being the alcohols.

Our reaction with the alcohols is carried out by adding the powderedsolid reaction product, described above to the alcohol in a suitablemixing vessel of acid resistant material at an initial temperature ofabout 30 an hour or until the reaction ceases. The alcohol is in aliquid or molten condition at the start, so that the mixture of samewith the powdered solid reagent takes the form of a thick pasty liquidat first, but becomes solid as the reaction progresses. The temperaturerises, but should preferably be held below about 60 or 80 C. by suitablecooling means until the reaction is completed. Evolution of hydrochloricacid gas occurs. We preferably use an excess of the reagent amounting toone fourth to one half more than the theoretically calculated quantityin order to secure rapid and complete action. At least 90 per cent .ofthe alcohol is sulfated under these conditions, and usually 9501 96 percent. In sulfating with ordinary liquid sulfating agents it is rarelypossible to obtain over" 90' per' centsulfation,

and an excess of reagent usually causes undesired side reactions.

A ball mill, suitably constructed to provide for cooling and for removalof hydrochloric acid gas formed in the reaction, is one suitable type ofmixer both for preparing our reagent and for the reaction with thealcohols, but other types may also be used. This mill serves not onlyfor mixing but for pulverizing the products.

The reaction may be represented as follows,

assuming that the HClSO3-NaCl reaction product is mainly thechlorsulfonate, and R being th alkyl radical of an alcohol.

+ HCl ROH NaClSO; RNaSO; (Alcohol) (Sodium (Sodium chlorsulalkyl fonate)sulfate) Any excess of reagent used is subsequently neutralized bytreating with a neutralizing agent consisting of finely ground metaloxide, hydroxide or carbonate in sufficient quantity to neutralize anyacidity in the mixture, thus obtaining a solid product which when usedin aqueous solution is found to have excellent wetting, sudsing,emulsifying and detergent properties without further purification. Ofcourse the reaction mixture could also be neutralized by mixing with asolution or slurry of a metal oxide, hydroxide, or carbonate, especiallyif the product is to be used im- 5 mediately in the wet condition, butthe dry neutralization as described is preferable, especially if theproduct is to be stored or shipped. Usually the same metal would beselected for neutralizing excess reagent as was used in making thereaction product, but in any event it should be one that does not forminsoluble reaction products, either when dry or when added to water foruse. The neutralized excess reagent may be allowed to remain in theneutralized product, as it is harmless for ordinary uses, or it may beremoved by a C. and stirring for about purification process as describedbelow. The product, however, tends to decompose if left in an acidcondition for any length of time unless protected from moisture, andshould therefore be neutralized or made slightly alkaline to stabilizeit. The amount of neutralizing agent thus required is much less thanwhen the alcohol is sulfated in the usual manner with chlorsulfonicacid, for example, as in this case, all the sulfating agent used must beneutralized, including both that portion reacting to form esters and anyexcess of reagent present.

If a purer form of product is desired it may be treated, afterneutralization with petroleum ether or other suitable organic solvent toremove unsulfated organic material; it may also be purified, either withor without previous removal of unsulfated organic material, bydissolving in ethyl alcohol or other suitable solvent of the sulfatedalcohol salt, filtering from inorganic and other impurities, and thesolvent then removed by evaporation.

Example 1 58 parts of sodium chloride and 58 parts of chlorsulfonic acidare mixed for about fifteen minutes or until the reaction is completewhile keeping the temperature below about 50 C. in a suitable mixingapparatus and the product is ground to a powder. These proportionsprovide a considerable excess of sodium chloride. The pulverized solidreagent thus produced is mixed with parts of a mixture of the alcoholsobtained by the catalytic reduction of coconut oil by hydrogen underhigh pressure, said alcohols having an average molecular weight of 208.The mixture is stirred in an acid resisting vessel, 'wh'ile protectedfrom moisture and keeping the mixture cooled to about 60 C., until thereaction is substantially complete. The resulting mixture is a solidwhich can readily be reduced to powder form. To this mixture is addedsolid sodium carbonate containing about 26 parts of actual sodiumcarbonate and thoroughly mixed. The result is a neutral or alkalinepowder perfectly stable under ordinary storage conditions and whosewater solutions have excellent wetting, sudsing, emulsifying anddetergent properties.

Other higher aliphatic alcohols may be substituted, such as for exampleparts of the alcohols derived from tallow by catalytic reduction, orparts of the alcohols obtained from sperm oil by known methods. Alsoother metals than sodium or potassium may be used both in forming thesulfating reagent and in neutralizing, such metals .as manganese,magnesium and nickel being especially suitable.

Example 2 Example 3 The product of Example 1 was extracted withpetroleum ether to remove organic impurities and then dissolved in ethylalcohol, filtered, and

252. COMPOSITIONS, 3 5 3 UTOSS crystallized by evaporation of the ethylalcohol. The product was a white, solid powder having very superiorwetting, sudsing, emulsifying and detergent properties.

Our procedure affords a new reaction for preparing Wetting, sudsing,emulsifying and detergent agents consisting essentially of salts ofsulfated higher aliphatic alcohols, which has important advantages overthe wet procedures hitherto used. The necessity or difficulty ofmaintaining the reaction vessel liquid-tight is greatly minimizedbecause of the viscous to solid condition of the reacting mixture in itsvarious stages. The sulfating operation, the neutralizing of any excessof the acid reagent used, and the final pulverizing can be carried outconveniently in the same mixing vessel. The full amount of both alcoholand sulfating reagent may be added at one time, whereas in the wetprocess the sulfating agent, such as chlorsulfcnic acid, must be addedto the alcohol slowly over a long period of time in order to keep thetemperature down to the required point, while if added too slowly someof the sulfated product first formed is destroyed. The older processinvolves danger in that if. through the breakage of a valve or otheraccident the acid flows into the alcohol too fast, this would cause aserious rise of temperature, resulting in undesirable side reactions andeven possible explosion. We obtain a higher percentage of sulfation withgreater freedom from unde sired side reactions. Our process isconsiderably more economical than the prior processes involving firstsulfating with an acid and then neutralizing with an alkali because ourreagents consist of chlorsulfonicacid, sodium chloride (or sulfate) anda small amount of sodium carbonate, as compared with chlorsulfonic acid,and sodium hydroxide or carbonate. In other words, we have in effectreplaced the sodium hydroxide or carbonate mainly with sodium chloride,which is much cheaper.

The product made by our process if protected from moisture even withoutneutralization is sufficiently stable to be allowed to rest for severaldays if necessary before final neutralization, whereas sulfated alcoholsprepared with chlorsulfonic acid and other liquid sulfating agents arevery unstable and must be neutralized immediately to preventdecomposition; they cannot even' be allowed to stand over night beforeneutralization without serious decomposition. Our product needs nofurther drying, after preparation as described, but can be stored orshipped in its condition immediately after neutralizing, whereas intheusual wet process the product must be dried, which involves not only anadditional expense but also a certain amount of decomposition and loss.

Having thus described our invention, what we claim and desire to secureby Letters Patent is:

1. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting an aliphatic alcohol containing ten totwenty-two carbon atoms per molecule with a solid reagent consisting ofthe reaction product of chlorsulfonic acid on a metal salt of the groupconsisting of chloride and sulfate, said metal being one which forms inthe said reaction a salt of the sulfuric ester of the said alcohol whichis soluble in water.

2. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting an aliphatic alcohol containing ten totwenty-two carbon atoms per molecule with a solid reagent consisting ofthe reaction product of chlorsulfonic acid on a metal salt of the groupconsisting of chloride and sulfate, the product thus obtained beingneutralized by further treatment with a solid neutralizing agentselected from the group consisting of metal oxides, hydroxides, andcarbonates, said metals being ones which form salts of the sulfuricester of said alcohol which are soluble in water.

3. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting alcohols derived from a natural fat bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a metal salt of the group consisting ofchloride and sulfate, the product thus obtained being neutralized byfurther treatment with a solid neutralizing agent selected from thegroup consisting of metal oxides, hydroxides, and carbonates, saidmetals being ones which form salts of the sulfuric esters of saidalcohols which are soluble in water.

4. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting alcohols derived from coconut oil bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a metal salt of the group consisting ofchloride and sulfate, the product thus obtained being neutralized byfurtlfer treatment with a solid neutralizing agent selected from thegroup consisting of metal oxides, hydroxides, and carbonates, saidmetals being ones which form salts of the sulfuric esters of saidalcohols which are soluble in Water.

5. A process for making wetting, sudsing, ;f-

emulsifyinganddetrgent agents comprising reacting an aliphatic alcoholcontaining ten to twenty-two carbon atoms per molecule derived fromoxidized paraffin hydrocarbons with a solid reagent consisting of thereaction product of chlorsulfonic acid on a metal salt of the groupconsisting of chloride and sulfate, the product thus obtained beingneutralized by further treatment with a solid neutralizing agentselected from group consisting of metal oxides, hydroxides, andcarbonates, said metals being ones which form salts of the sulfuricester of said alcohol which are soluble in water.

6. A process for makingwetting, sudsing, emulsifying and detergentagents comprising reacting alcohols derived from a natural fat bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a metal salt of the group consisting ofchloride and sulfate, the product thus obtained being neutralized byfurther treatment with a solid neutralizing agent selected from thegroup consisting of metal oxides, hydroxides, and carbonates, saidmetals being ones which form salts of the sulfuric esters of saidalcohols which are soluble in water, said neutralized product beingpurified by washing with a suitable organic solvent to remove unsulfatedorganic material.

7 A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting alcohols derived from a natural fat bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a metal salt of the group consisting ofchloride and sulfate, the product thus obtained being neutralized byfurther treatment with a solid neutralizing agent selected from thegroup consisting of metal oxides, hydroxides, and carbonates, saidmetals being ones which form salts of the sulfuric esters of saidalcohols which are soluble in water, said neutralized product beingpurified by dissolving in a suitable organic solvent, separating frominsoluble inorganic and other impurities and removing said solvent by 5evaporation.

8. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting alcohols derived from coconut oil bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonio acid on a sodium salt of the group consistingof chloride and sulfate, the product thus obtained being neutralized byfurther treatment with a solid neutralizing agent selected from thegroup consisting of sodium oxide, hydroxide or carbonate,

said neutralized product being purified by washing with a suitableorganic solvent to remove unsulfated organic material.

9. A process for making wetting, sudsing, emulsifying and detergentagents "comprising reacting alcohols derived from coconut oil bycatalytic reduction with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a 7 35 acting an aliphatic alcoholcontaining ten to twenty-two *c'arbon atoiiffpfir molcul''derived fromoxidized petroleum with a solid reagent consisting of the reactionproduct of chlorsulfonic acid on a metal salt of the group consisting ofchloride and sulfate, the product thus obtained being neutralized byfurther treatment with a solid neutralizing agent selected from thegroup consisting of metal oxides, hydroxides, and carbonates, saidmetals being ones which form salts of the sulfuric ester of said alcoholwhich are soluble in water, said neutralized product being purified bywashing with a suitable organic solvent to remove unsulfated organicmaterial.

11. A process for making wetting, sudsing, emulsifying and detergentagents comprising reacting an aliphatic alcohol containing ten totwenty-two carbon atoms per molecule derived from oxidized petroleumwith a solid reagent consisting of the reaction product of chorsulfonicacid on a metal salt of the group consisting of chloride and sulfate,the product thus obtained being neutralized by further treatment with asolid neutralizing agent selected from the .group consisting of metaloxides, hydroxides, and

carbonates, said metals being ones which form salts of the sulfuricester of said alcohol which are soluble in water, said neutralizedproduct being purifledby dissolving in a suitable organic solvent,separating from insoluble inorganic and by the presence of moleculeshaving from twelve to twenty-two carbon atoms each, toreact with thereaction product oi chlorsulfonic acid .on a metal salt of the groupconsisting of chloride. and sulfate, said metal being one which formswatersoluble products orsaiamcohaism said reaction.

ARNON O. SNODDY. W ILFRED S. MARTIN.

